Trends and Analysis of Major Ions at Russian EMEP Stations (2002-2012)

This research study by Alisa Trifonova-Iakovleva focuses on the trends of major ions at Russian EMEP stations from 2002 to 2012. The analysis includes time series for different locations such as Danki, Janiskoski, and Pinega, examining air and wet concentrations as well as depositions. The structure of trend analysis involves average values, raw data, and methods like Mann-Kendall test and quantile regression. The results suggest no significant trend in the data analyzed, with insights into quantile regression and outlier analysis provided.

• Trends
• Major Ions
• Russian EMEP Stations
• Analysis
• Time Series

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1. Trends for major ions at Russian EMEP stations for period 2002 2012 Alisa Trifonova-Iakovleva

2. EMEP stations in RUSSIA

3. Time series for analysis Danki (2002-2012): - air concentration SO2, SO42-, NO3-,NH4+ - wet concentration SO42-, NO3-,NH4+ - wet deposition Janiskoski (2002-2012): - wet concentration - wet deposition Pinega (2002-2012): - wet concentration - wet deposition

4. Structure of trend analysis Average values (MAKESENS) - whole time series concentrations - season concentrations Raw data (R) - whole time series concentrations - seasons concentrations - whole time series depositions - seasons depositions

5. Methods of analysis Mann-Kendall test, Sen s slope for average values Outlier analysis, least square, quantile regression (incl. trends in upper quantiles) for raw data Comparison of results Significant Mann-Kendall test? YES NO Significant Least Square or quantile regression? YES Lsq&q.r. in CI of results of Sen s method? YES Add information (majority of results) (only 1 case) NO Keep the result of Mann-Kendall test No significant trend NO No trend

6. Quantile regression -QUANTILE REGRESSION min ??? ?? ??? + 1 ?? ??? ? {?:?? ???} ? {?:?? ???} MEDIAN REGRESSION =1 2 1 2min ? ? ?? ??? ? Roger Koenker; Gilbert Bassett, Jr. Roger Koenker (2015). http://CRAN.R-project.org/package=quantreg Regression Quantiles , Econometrica, Vol. 46, No. 1. (Jan., 1978), pp. 33-50 quantreg: Quantile Regression. R package version 5.11.

7. Example of quantile regression

8. Results of upper quantile regression Majority of directions of upper quantiles trends similar to usual trend Very few other cases

9. DANKI air Time series, ug S/m^3 SO2 DJF SO2 MAM SO2 JJA SO2 SON SO2 YR SO4 DJF SO4 MAM SO4 JJA SO4 SON SO4 YR NH4 DJF NH4 MAM NH4 JJA NH4 SON NH4 YR NO3 DJF NO3 MAM NO3 JJA NO3 SON NO3 YR Signific. Q Upper Quant LSq Quant.regr * -0,04278 -0,02783 -0,00603 0,004476 -0,01113 -0,02382 -0,02205 0,006235 0,008343 0,004202 -0,02925 -0,03582 0,001213 0,010965 -0,01289 -0,0079 -0,01634 0,009675 0,006174 0,008635 - - -0,01461 -0,00365 -0,00365 -0,00365 -0,00731 0,025568 -0,00731 - - - - -0,01826 -0,01096 -0,01461 -0,01461 0,021915 0,00365 0,00365 - 0,00365 ** down - - - down down - - - down down down down down up - - - up -0,01289 -0,00297 - - - -0,02088 0,008561 - - -0,0071 -0,02604 -0,01722 -0,01567 -0,01668 0,026064 - 0,004456 - 0,008189 + * Average data Raw data

15. Outlier analysis Not easy to understand if the point is outlier Only several points for whole time series No significant effect on the result LSq Quant.regr Outliers LSq\outl Quant.regr \outl 0,010 0,011 7 0,009 0,011 mg-N/l/year

16. ADDITION

17. Trends in upper quantiles No trend for MS, Lsq Upper quantiles decrease Increasing trend for MS, Lsq Upper quantiles increase

18. DANKI wet Time series SO4-S DJF SO4-S MAM Signific. Q Upper Q - - LSq - -0,0301 Quant.regr - -0,03653 Upper Q - - LSq - - Quant.regr - - -0,04136 -0,00787 SO4-S JJA -0,00169 down -0,03141 - - - - SO4-S SON 0,009076 - - - - - -0,06575 SO4-S YEAR 0,000725 down -0,01882 -0,00731 - - - NO3-N DJF NO3-N MAM NO3-N JJA NO3-N SON NO3-N YEAR NH4-N DJF NH4-N MAM NH4-N JJA -0,02692 -0,00682 0,007924 0,005486 0,002773 -0,04456 0,001887 0,009819 - - - - - - - - - - - - - up - - - - up? up? up? 0,028307 - - - - 0,033238 - - - - - - - - - - 0,018263 - - 0,01461 - 0,018263 0,009643 - 0,010421 - - + NH4-N SON -0,00638 - - - down -0,10227 -0,0694 NH4-N YEAR 0,003831 - - - down-up - -

19. PINEGA wet Time series, mg/l SO4-S DJF Quant. regr -0,01096 Quant. regr - Signific. Q Upper Q LSq Upper Q LSq 0,000872 down -0,02118 - - SO4-S MAM -0,01347 down -0,03901 -0,03653 - - - SO4-S JJA -0,0083 up 0,045072 - up - 0,11688 SO4-S SON -0,00242 - - - - - - SO4-S YEAR -0,00491 down -0,01596 -0,00731 up - - NO3-N DJF NO3-N MAM NO3-N JJA ** 0,018151 up 0,020892 0,021915 up 0,046387 0,032873 0,00354 - - - - - - * 0,011905 up 0,244718 0,01461 up 0,10227 0,04383 NO3-N SON 0,004643 - - - up 0,018263 0,01461 NO3-N YEAR NH4-N DJF NH4-N MAM NH4-N JJA * 0,010867 up 0,01019 0,010958 up 0,036525 0,025568 0,020199 - - - up 0,069763 0,032873 0,020055 - - - - - - * 0,015439 up 0,109575 0,040178 up 0,295853 0,124185 NH4-N SON 0,019002 - 0,01461 0,018263 up 0,08766 0,036525 NH4-N YEAR ** 0,019741 up 0,01938 0,021915 up 0,091313 0,04383

20. JANISKOSKI wet Time series, mg/l Signifi c Upper Quantile Upper Quantile Q LSq Quant.regr LSq Quant.regr SO4-S DJF SO4-S MAM SO4-S JJA -0,01738 - -0,02177 -0,01096 down -0,09643 -0,05844 -0,02172 - - - - - -0,08766 0,006364 up 0,036525 - - - -0,11688 SO4-S SON SO4-S YEAR NO3-N DJF NO3-N MAM NO3-N JJA -0,01181 down -0,01132 -0,00731 down -0,12784 -0,05479 -0,0082 up - -0,01096 down-up -0,08985 -0,0767 -3,5E-05 - - - down -0,01972 - -0,00615 - - - - - - 0,002082 up 0,009862 - - - - NO3-N SON NO3-N YEAR NH4-N DJF NH4-N MAM NH4-N JJA -0,00035 up 0,006209 0,003653 down - - -0,00092 up 0,010227 0,003653 down - - -0,01475 down -0,02922 -0,01096 down -0,09131 -0,02192 -0,00479 - - - - - - 0,001757 up 0,020454 0,010958 up - 0,021915 NH4-N SON -0,00513 down -0,01717 - down -0,10373 -0,02557 NH4-N YR -0,00355 down - 0,003653 down -0,05479 -

21. PINEGA+OUTLIER ANALYSIS Time series, mg/l SO4-S DJF SO4-S MAM SO4-S JJA SO4-S SON SO4-S YEAR NO3-N DJF NO3-N MAM NO3-N JJA NO3-N SON Quant. regr Outliers LSq\outlQuant.re Quant. regr Outliers LSq\outlQuant.re Signific. Q Upper Q LSq Upper Q LSq gr\outl gr\outl 0,000872 down - - 1 -0,02118 -0,01096 - - - - - - down - - - -0,01347 -0,03901 -0,03653 - - - - - - up 1 up 2 -0,0083 0,045072 - 0,036525 - - 0,11688 - 0,109575 - 7 - 6 -0,00242 - - - - - - - - down 1 up 4 -0,00491 -0,01596 -0,00731 -0,01717 -0,07305 - - - - up 2 up 1 ** 0,018151 0,020892 0,021915 0,020089 0,021915 0,046387 0,032873 - - - - - - 0,00354 - - - - - - - - up 2 up 2 * 0,011905 0,244718 0,01461 0,178973 0,01461 0,10227 0,04383 0,06538 0,040178 - - up 7 0,004643 - - - - 0,018263 0,01461 - 0,010958 NO3-N YEAR NH4-N DJF NH4-N MAM NH4-N JJA NH4-N SON up 7 up 4 * 0,010867 0,01019 0,010958 0,009204 0,010958 0,036525 0,025568 0,032873 0,025568 - - up 3 0,020199 - - - - 0,069763 0,032873 0,045875 0,032873 - - - - 0,020055 - - - - - - - - up - up - * 0,015439 0,109575 0,040178 - - 0,295853 0,124185 - - - 2 up 6 0,019002 0,01461 0,018263 0,014464 0,018263 0,08766 0,036525 0,050258 0,036525 NH4-N YEAR up 4 up - ** 0,019741 0,01938 0,021915 0,018628 0,021915 0,091313 0,04383 - -

22. JANISKOSKI wet+OUTLIER Time series, mg/l SO4-S DJF SO4-S MAM SO4-S JJA SO4-S SON SO4-S YEAR NO3-N DJF NO3-N MAM NO3-N JJA NO3-N SON NO3-N YEAR NH4-N DJF NH4-N MAM NH4-N JJA NH4-N SON NH4-N YR Quant.re gr Outliers LSq\outlQuant.re Quant.regr\o utl Signific. Q Upper Q LSq Upper Q LSq Quant.regr Outliers LSq\outl gr\outl - 2 down - -0,01738 -0,02177 -0,01096 -0,01045 -0,01096 -0,09643 -0,05844 - - - 4 - 3 -0,02172 - - - - - -0,08766 - -0,0767 up 4 - - 0,006364 0,036525 - 0,019724 - - -0,11688 - - -0,01181 down -0,01132 -0,00731 2 down - -0,01242 -0,00731 -0,12784 -0,05479 - - up - down-up - -0,0082 - -0,01096 - - -0,08985 -0,0767 - - - - down - -3,5E-05 - - - - -0,01972 - - - - 1 - 1 -0,00615 - - - - - - - - up 4 - 3 0,002082 0,009862 - 0,003653 - - - - - up - down 1 -0,00035 0,006209 0,003653 - - - - - - up 7 down 2 -0,00092 0,010227 0,003653 0,005114 0,003653 - - -0,00986 - -0,01475 down -0,02922 -0,01096 - down 2 - - -0,09131 -0,02192 -0,07378 -0,01826 - - - 1 -0,00479 - - - - - - - - up 3 up 6 0,001757 0,020454 0,010958 0,019358 0,010958 - 0,021915 0,036525 0,018263 -0,00513 down -0,01717 - down - - - - -0,10373 -0,02557 - - -0,00355 down 4 down - - 0,003653 - 0,003653 -0,05479 - -0,04018 -